Organometallic compounds and polymers made therefrom

ABSTRACT

Compounds of formula (I) are disclosed: ##STR1## wherein L 1  is a main group atom, L 2  is a neutral ligand, M is a transition element or a metal element of Group 13, 14, 15, or 16 of the Periodic Table, x is the number of coordination sites of M, R 1  is a polymerizable group, R 2 , R 3 , and R 4  are ligands, and R 5  is an anionic ligand. The compounds or monomers of formula (I) are capable of conversion to polymers by combination with one or more other known monomers, such as methyl methacrylate. Such polymers can then be added as a binder in a paint formulation to make marine antifouling coating compositions. Also described is a method to prevent fouling on surfaces wherein a composition containing a metal complex compound of formula (II): ##STR2## wherein M, x, L 2 , n, and R 4  have the same meaning as in formula (I), is applied to the surface susceptible to fouling.

BACKGROUND OF THE INVENTION

The present invention relates to novel compounds that are particularlyuseful in marine antifoulant coating compositions.

Marine fouling on ships and marine structures has been a problem forthousands of years. This problem has been recently addressed primarilyby the use of certain coatings containing biocides that are toxic tomarine organisms. These conventional coatings leached biocides out ofthe coating when in seawater.

Such a paint system, however, fails to provide a desired constanttoxicant release, and moreover, does not advantageously erode inservice. This is due to the selective extraction of the water-solublecomponent and consequent leaching of the toxicant from the interior ofthe paint film. A matrix of the insoluble resin component remains behindafter the water-soluble component of the film (gum rosin) is leachedaway. Moreover, the spent paint film no longer controls fouling eventhough it might contain up to 30-40% of the initial level of toxicantbecause water penetration required for leaching the toxicant to thesurface is limited through the matrix of residual resin. Spentantifouling systems of this type do not provide a suitable base forrepainting since they possess poor mechanical properties due to thevoids in the film resulting in poor adhesion of the new paint film.

Attempts to incorporate toxicants into water soluble polymers and to usethese as antifouling paints have also failed to produce the desiredresults. Such paints swell in seawater and cannot be expected to providegood mechanical properties and uniform control of fouling since thewhole paint film is weakened on prolonged water immersion.

In recent years, so-called self-polishing antifouling coatings havebecome increasingly popular. These coatings are based on polymers oftributyltin methacrylate, methyl methacrylate, and film softeningmonomers such as 2-ethylhexyl acrylate. The organotin polymer acts asthe paint binder. All such paints also contain a toxicant additive suchas cuprous oxide or a triorganotin compound. In addition, the usualpaint additives such as pigments, thixotropic agents, etc. may also bepresent. In normally alkaline seawater, the polymeric organotin binderis gradually hydrolyzed and the tributyltin is liberated in a form thatis an active antifoulant. The hydrolyzed polymer formed is water-solubleor water-swellable and is easily eroded off the surface by movingseawater, exposing a fresh surface of paint. The major advantage ofthese systems is that, unlike leaching paints, toxicant release islinear with time and all of the toxicant present is utilized over thelifetime of the paint. Furthermore, there is no need to remove theresidues of an old self-polishing paint system prior to repainting,since the composition of the residue is essentially the same as it waswhen originally applied unlike conventional antifouling paints whichleave a weak, leached-out matrix of binder on the ships' hull at the endof their lifetime. An additional advantage claimed for such systems is areduction in hull surface roughness with time as a consequence oferosion of the paint film. This roughness reduction translates to fuelsavings for the ship operator.

Sea-going vessels usually have between 2 and 4 coats of antifoulingpaint, each coat of 100 microns film thickness, applied to the hull.This coating, of 200 to 400 microns total film thickness, is expected tolast for about five years.

A marine antifoulant coating should preferably meet some criteria inorder to be commercially acceptable, such as:

1. The polymer is preferably soluble in a paint media for easyapplication;

2. The polymer solution preferably has good film-forming properties;

3. The film coating preferably has good adhesion to the ship's surfaceand is flexible;

4. The film preferably undergoes hydrolysis only at the coating surface.This permits the controlled release of the metal. The remaining paintsurface becomes susceptible to the moving seawater and is eroded. Thismechanism is known as "self-polishing" and a marked improvement in theship's fuel efficiency is observed; and

5. The polymer preferably has controlled release characteristics.

Accordingly, the present invention is directed to novel compounds andmarine antifoulant coating compositions containing polymers polymerizedfrom these compounds.

Additional features and advantages of the present invention will be setforth in the description which follows, and in part will be apparentfrom the description, or may be learned by practice of the presentinvention. The objectives and other advantages of the present inventionwill be realized and attained by means of the elements and combinationsparticularly pointed out in the written description and appended claims.

SUMMARY OF THE INVENTION

To achieve these and other advantages and in accordance with the purposeof the present invention, as embodied and broadly described herein, thepresent invention relates to a compound of formula (I): ##STR3## In thisformula, L¹ is a main group atom. M is a transition element of thePeriodic Table. Alternatively, M is a metal element of Group 13, 14, 15,or 16 of the Periodic Table. x is the oxidation state of M, n is thenumber of coordination sites on M, and m represents the number of (R¹ R²R³) L¹ ligands bonded to M, which is usually 1.

R¹ is a polymerizable group.

R² and R³, which can be the same or different, are a substituted orunsubstituted alkyl of up to 15 carbons; a substituted or unsubstitutedaryl of up to 30 carbons; a substituted or unsubstituted alkoxy orthioalkyl of up to 15 carbons; a substituted or unsubstituted aryloxy orthioaryl of up to 20 carbons; an oxygen or sulfur containing heterocycleof up to 25 carbons; a substituted or unsubstituted amine; a substitutedor unsubstituted amide; or a substituted or unsubstituted nitrogenheterocycle of up to 25 carbons when L¹ is not N.

R⁴ is an anionic ligand and can be the same or different when x isgreater than 1.

Lastly, L² is a neutral ligand group.

In another aspect, the present invention includes polymerizing one ormore of the above compounds of formula (I) for use in marine antifoulantcoatings as a binder which may also be effective as a co-biocide.

The present invention also relates to controlled release compositionscontaining polymers obtained by polymerizing monomers of formula (I).

In addition, the present invention relates to methods to prevent foulingon surfaces by applying a composition containing a compound of formula(II): ##STR4## wherein M, x, L², n, and R⁴ have the same meanings as informula (I).

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not intended to provide further explanation of the presentinvention, as claimed.

DETAILED DESCRIPTION

One aspect of the present invention relates to the novel compounds offormula (I): ##STR5##

Compounds of formula (I) can also be considered monomers since thesecompounds are capable of conversion to polymers by combination with thesame monomer or any other monomers capable of addition to the polymer.Polymers resulting from the polymerization of one or more compounds offormula (I) with any other known monomer, such as methyl methacrylate,can then be added as a binder in a paint formulation to make marineantifouling coating compositions.

Referring to formula (I), L¹ is a main group atom or element thatpreferably is a Group 15 element of the Periodic Table. L¹ can also be aGroup 13, 14, or 16 element of the Periodic Table. All groups of thePeriodic Table referred to herein are with reference to the "NewNotation" of the Periodic Table set forth in Hawley's Condensed ChemicalDictionary 11th Ed. Thus, L¹ is preferably nitrogen, phosphorus,arsenic, antimony, or bismuth. Most preferably, L¹ is phosphorus.

m represents the number of (R¹ R² R³) L¹ ligands bonded to M. m isusually 1 except for the following exceptions.

m is 2 when M is Cu, x is 1, L¹ is phosphorus, L² is not present (i.e.,n-(x+m) is zero) and R⁴ is cyanate, thiocyanate, and isocyanate; and

m is 3 when M is Cu, x is 1, L¹ is phosphorus, L² is not present (i.e.,n-(x+m) is zero), and R⁴ is a substituted or unsubstituted thioalkylhaving up to 15 carbons or a substituted or unsubstituted thioarylhaving up to 25 carbons.

M is a transition element of the Periodic Table (i.e., Groups 3-12 ofthe Periodic Table).

Alternatively, M is a metal element of Groups 13-16 of the PeriodicTable. In other words, M can be Sc, Y, La, Ac, Ti, Zr, Hf, V, Nb, Ta,Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au,Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, Si, As, Te, or Po.

Preferably, M is copper, zinc, or tin. Most preferably, M is copper.

x represents the oxidation state of M. n is the number of coordinationsites on M. As presently known with regard to coordination sites inexisting elements encompassed by M, n can be a whole number from 2 to 9depending on M. For instance,

where M is a Group 3 element, which includes Sc and Y,

M has a coordination number of either 4 or 6 (mainly 6); and

M has an oxidation state of +2, +3, +4 (mainly +3).

where M is a Group 4 element,

M has a coordination number of 4, 5, 6, 7, or 8 (mainly 4 or 6); and

M has an oxidation state of +4.

where M is a Group 5 element,

M has a coordination number of 4, 5, 6, 7, 8, or 9 (mainly 6); and

M has an oxidation state of +3, +4, or +5.

where M is a Group 6 element,

M has a coordination number of 3, 4, 5, or 6 (mainly 6); and

M has an oxidation state of +2, +3, +4, +5, or +6 (mainly +2 and +3).

where M is a Group 7 element, which includes Mn, Re, and Tc,

M has a coordination number of 4, 5, 6, or 7 (mainly 4 and 6); and

M has an oxidation state of +2, +4, +5, or +7.

where M is a Group 8 element,

M has a coordination number of 3, 4, 5, 6, 7, or 8 (mainly 6); and

M has mainly oxidation states of +2, +3, +4, and +6.

where M is a Group 9 element,

M has a coordination number of 4, 5, or 6; and

M has mainly oxidation states of +1, +2, +3, or +4.

where M is a Group 10 element,

M has a coordination number of 4 or 6; and

M has mainly oxidation states of +2 and +4.

where M is a Group 11 element,

M has a coordination number of 2, 4, or 6; and

M has mainly oxidation states of +1 and +2.

where M is a Group 12 element,

M has a coordination number of 2, 4, or 6; and

M has an oxidation state of +2.

where M is a Group 13 metal element, which includes Al, Ga, In, and Tl,

M has a coordination number of 3, 4, 5, or 6; and

M has an oxidation state of +2 or +3 (mainly +3).

where M is a Group 14 metal element, which includes Si, Ge, Sn, and Pb,

M has a coordination number of 4, 5, or 6; and

M has an oxidation state of +2 or +4.

where M is a Group 15 metal element which includes As, Sb, and Bi,

M has a coordination number of 3, 4, 5, or 6; and

M has an oxidation state of +3 or +5.

where M is a Group 16 metal element, which includes Te and Po,

M has a coordination number of 4, 5, or 6; and

M has an oxidation state of +2, +4, or +6.

R¹ is a polymerizable group. In other words, R¹ will be a substituentwhich will be polymerizable when the compound of formula (I) ispolymerized into a polymer. For purposes of the present invention, R¹can be any type of polymerizable group. This includes:

(1) Any unit with a double bond and is given by the following formula:##STR6## where R⁶ is a hydrogen; an alkyl group with up to 25 carbons;an olefin group with up to 25 carbons; and R⁷ is a hydrogen; asubstituted or unsubstituted alkyl with up to 25 carbons; a substitutedor unsubstituted aryl with up to 25 carbons; a halogen; a substituted orunsubstituted carboxylic group with up to 25 carbons; a substituted orunsubstituted amide group with up to 25 carbons; a cyanate; isocyanate;or a thiocyanate. In this unit, the substituents R⁶ or R⁷, preferably R⁷bond to L¹.

(2) Cyclic monomers which polymerize either through a double bond withinthe ring or by ring opening polymerization (ROMP). These include ringswith three to eight members and the atoms within the ring aresubstituted and unsubstituted carbons, carbonyl, oxygen, substituted orunsubstituted phosphorus, or substituted or unsubstituted amides. Thetotal number of carbons can be up to 40.

(3) Monomers with coreactive functional groups which can include thefollowing:

H₂ N--R⁸ --NH₂

HO₂ C--R⁹ --CO₂ H

H₂ N--R¹⁰ --CO₂ H

HO--R¹¹ --OH

Cl--R¹² --Cl

ClOC--R¹³ --COCl

where R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹³ are independently selected from asubstituted or unsubstituted alkyl with up to 25 carbons; a substitutedor unsubstituted aryl with up to 25 carbons; a substituted orunsubstituted silane with up to 25 carbons; a substituted orunsubstituted nitrogen heterocycle with up to 25 carbons. In addition,R⁸ can also be carbonyl. With these coreactive functional groups, the Rgroups (i.e., R⁸ through R¹³) bond to L¹.

Preferably, R¹ is an acrylate or methacrylate group.

R² and R³ which can be the same or different is a substituted orunsubstituted alkyl of up to 15 carbons; a substituted or unsubstitutedaryl having up to 30 carbons; a substituted alkoxy or thioalkyl of up to15 carbons; a substituted or unsubstituted aryloxy or thioaryl having upto 20 carbons; oxygen or sulfur containing heterocycle with up to 25carbons; where L=N, the group can also consist of substituted andunsubstituted amines, amides, and nitrogen heterocycles (e.g., pyridine)with up to 25 carbons.

R² and R³ can alternatively interconnect to form a chelating ligand suchas catechol. The partial structure would be as follows: ##STR7##

Preferably, R² and R³ are alkyl or alkoxy groups of up to 15 carbons; oraryl or aryloxy groups of up to 25 carbons.

R¹⁴ is an alkyl group of up to 6 carbons or represents a bond between R²and R³, and preferably is a bond between R² and R³.

R⁴ is an anionic ligand. Examples of anionic ligands include, but arenot limited to, a halogen, a cyanate, an isocyanate, a thiocyanate, analkyl group that preferably does not contain an α- or β-hydrogen capableof undergoing elimination, a substituted or unsubstituted thioalkylhaving up to 15 carbons; a substituted or unsubstituted thioaryl havingup to 25 carbons; a sulfur containing heterocycle with up to 25 carbons;a substituted or unsubstituted aryloxide with up to 25 carbons; asubstituted or unsubstituted alkoxide with up to 15 carbons; an oxygencontaining heterocycle with up to 25 carbons; a substituted orunsubstituted cyclopentadienyl with up to 30 carbons; and anacetylacetonate with optional substitution of at least one of any of thehydrogens on any of the carbons therein with a halogen. When x is 2 orhigher, R⁴ can be the same or different.

Preferably, R⁴ is a halogen, a cyanate, an isocyanate, or a thiocyanate.

L², when it exists, is a neutral ligand. For example, L² can be the sameor different when [n-(x+m)] is two or greater. L² can be a trivalentphosphorus, trivalent arsenic, trivalent antimony compound or a divalentsulfur or divalent selenium or a divalent tellurium compound when bondedto either three (for trivalent compounds) or two (for divalentcompounds) substituents (excluding the bond to M) which can be the sameor different. These divalent or trivalent compounds, for example, canhave substituents such as a halogen, a substituted or unsubstitutedaryloxy or alkyloxy of up to 25 carbons, a substituted or unsubstitutedalkyl, a substituted or unsubstituted aryl.

Alternatively, L² is a substituted or unsubstituted aryl or alkylisocyanide; a carbonyl or carbon monoxide; a thiocarbonyl or carbonmonosulfide; a nitrosyl; a substituted or unsubstituted amine; a nitrilewith a substituted or unsubstituted alkyl or aryl; a coordinatingsolvent such as cyclic or linear ethers which include tetrahydrofuran(THF); a substituted or unsubstituted unsaturated alkyl or aryl whichbonds to the M mainly through a π-bond.

When n-(x+m) is greater than 0 (i.e., 1 or higher), L² substituents willbe attached to M due to the additional coordination sites of M. Whenthere is more than one L² substituent, each L² substituent can be thesame or different or chelating (i.e., interconnected). For instance,when M is chromium (III), n is six, x is three, m is one, and n-(x+m) istwo. There would be two L² substituents which could both be, e.g., anamine or one L² substituent could be an amine element and the other L²substituent could be phosphine.

A preferred formula of formula (I) is formula (II): ##STR8## wherein R¹⁵represents a hydrogen or a linear alkyl group of up to 6 carbons.

A most preferred compound has the following formula: ##STR9##

In this formula, M is Cu(I) metal which has biocidic effects in seawaterand X is Cl, SCN, or SPh (thiophenyl). When X is Cl, m=1; when X is SCN,m=2; and when X is SPh, m=3. L¹ is P which forms the phosphite portion.This phosphite portion maintains the +1 oxidation state of the Cu andhydrolyzes to an inorganic phosphate. The acrylate portion of thecompound is retained as the site for free-radical polymerization. Whenreleased, the phosphite portion further increases the acidity (i.e.,lowers the pH) near the polymer surface. Having a lower pH near thepolymer surface creates an undesirable environment to marine life, e.g.,barnacles. The above compound can also couple electrochemically with Cu₂O where the two Cu(+1) species convert to a Cu(O) and a Cu(+2) toprovide a more effective release of Cu.

For purposes of the present invention, the following definitions areapplicable to the terms as used in the present application.

An unsubstituted aryl group is defined to include at least one benzenering, whether fused or not. "Fused" means two or more aromatic benzenerings share at least one carbon atom, such as for example in the case ofbiphenyl or naphthyl groups.

A substituted aryl group is defined to include the addition to one ormore aryl ring carbons: at least one nitrogen-containing ligand, such asfor example an azide, imine, ketimine, amine, amide, or imide; at leastone oxygen-containing ligand, such as for example an alcohol, ether,ester, ketone, aldehyde, anhydride or organic acid such as carboxylic;at least one sulfur-containing ligand such as for example, a thiol,sulfide, disulfide, sulfone, sulfoxide, sulfonic ester, or sulfonicacid; substituted and unsubstituted alkyl groups such as defined in thisapplication.

With respect to substituted and unsubstituted aryl groups, this isintended to also include methyl, ethyl or other alkyl substitutionsincluding halogen substitutions and acyl halide carboxylic substitutionsthat are initiated by Friedel Crafts type catalysts. In other words anyelectrophilic or nucleophilic type reaction between an aryl and somesubstituent which leads to a product is intended to be covered as partof the substituted aryl group. Examples of such substituted aryl groupsare: 2,4,6-trimethyl styrene; alpha-methyl styrene; m-bromo-styrene; andm-methyl-styrene.

Unsubstituted alkyl groups, whether saturated or unsaturated, andcyclic, branched, or unbranched are intended to include primarilycompounds consisting essentially of only carbon and hydrogen. Examplesof such materials include ones that satisfy the formula C_(y) H_(2y+1)or C_(y) H_(2y-1) where y can vary, e.g., from 1 to 20. y is at least 3for cyclic alkanes, and y is at least 4 for branched cyclic alkanes.

Substituted alkyl groups, whether saturated or unsaturated and cyclic,branched, or unbranched, include materials that result from replacingone or more hydrogens of an unsubstituted "alkyl group" as definedherein with: at least one halogen, such as fluorine, chlorine, bromine,or iodine; at least one oxygen, nitrogen or sulfur, wherein the oxygenoptionally has at least one additional carbon, nitrogen, or sulfurattached to it; the nitrogen optionally has at least one additionalcarbon, nitrogen, or sulfur attached to it; and the sulfur optionallyhas at least one additional carbon, nitrogen, or sulfur attached to it.Examples of substituted alkyls include such compounds as amines,alcohols, acids, esters, ketones, sulfides, sulfones, sulfoxides,isocyanates, cyanates, thiocyanates, nitriles, and nitrosones.

With regard to the preparation of the above-described compounds offormula (I), there are a variety of methods which can be used.

Generally, a compound having the formula (III) ##STR10## is reacted witha compound having the formula (IV) ##STR11## L¹, R¹, R², and R³, informula (III) and M, L², R⁴, n, m, and x in formula (IV) have the samemeaning as in formula (I) described above. Z¹ represents a pair ofelectrons on L¹ or a functional group (i.e., leaving group). Generally,Z¹ is any functional group which is replaceable by the available bondsite from ##STR12## Examples of functional groups encompassed by Z¹include --OH, and halides. Z¹ will generally represent a pair ofavailable electrons on L¹ when L¹ is nitrogen, phosphorous, arsenic,antimony, or bismuth. When L¹ is not a Group 15 element of the PeriodicTable, such as sulfur or silicon, Z¹ can be a functional group such as--OH or a halide.

Compounds of formula (III) are generally commercially available fromsuch sources as Aldrich Chemical Co.

Specific examples as well as the preparation of compounds of formula(III) wherein L^(I) is phosphorous are described in Pudovik et al.,Chemical Abstract, Vol. 63, 1965 (p. 13420) with regard to itsdiscussion of phosphites. This reference is specifically incorporatedherein by reference.

With respect to the compounds of formula (IV), Z² represents an emptyorbital which has the proper orientation to accept the pair of electrons(Z¹) to form a L1--M bond. In addition, Z² can be a functional groupwhich can react with Z¹ to form an independent Z¹ Z² molecule and L¹ -Mbond. An example of such a functional group (i.e., leaving group) is ahydride group or a halide group. In such a case, the Z² functional groupwill bond with the Z¹ leaving group to form a compound and the compoundof formula (I) will be formed by the open bond site in L¹ and the openbond site in M^(x).

Furthermore, Z¹ can alternatively represent a pair of electrons, whileZ² represents a labile ligand group such as acetonitrile. In such acase, the acetonitrile is stable by itself and upon breaking off from M,a bond forms between L¹ and M^(x). Z² can also represent an emptyorbital position on M that can accept electrons from L¹ when Z¹represents a pair of electrons. One example of such a situation is whenM is Cu(I) and L² is Cl.

Examples of compounds of formula (IV) include, but are not limited to,CuCl, CuSCN, ZnCl₂. Compounds of this type are generally commerciallyavailable from such sources a Strem Chemical Co. and Aldrich ChemicalCo.

In view of the above, the description set forth below provides a moredetailed preparation of preferred compounds of formula (I) of thepresent invention.

Preparation of the compounds described below generally follows athree-step synthesis. First, sodium acrylate or methacrylate issynthesized from the reaction of acrylic or methacrylic acid with sodiumhydroxide. For example, the reaction scheme below shows a reaction ofmethacrylic acid with sodium hydroxide. ##STR13##

The sodium acrylate or sodium methacrylate, in turn, is reacted withchlorodiethylphosphite to give acrylodiethylphosphite ormethacryiodiethylphosphite. For example, the reaction scheme below showssuch a reaction for methacrylodiethylphosphite. ##STR14##

The acrylodiethylphosphite or methacrylodiethytphosphite, in turn andpreferably in situ, is reacted with CuX (X=Cl, SCN, SPh (thiophenyl)) toform Cu acrylodiethylphosphite or methacrylodiethylphosphite. Forexample, the reaction scheme below shows such a reaction for CuX andmethacrylodiethylphosphite. ##STR15##

Both of these phosphorous containing compounds are abbreviated herein asthe chemical symbol of the metal, here copper, followed by "P" and theword "monomer". Hence copper acrylophosphite is abbreviated as "PCuXmonomer" and the corresponding zinc metal monomer as "PZnX monomer". Asynthesis is described for CuCl, but the identical reactions apply forthe preparation of CuSCN and CuSPh as well as other metals encompassedby M.

The presence of unreacted acrylic or methacrylic acid, water, or CuX canlead to undesirable side reactions. Accordingly, the sodium acrylate ormethacrylate should be washed thoroughly to remove any unreacted acrylicor methacrylic acid. The remaining precipitate should then be dried(e.g., by means of a vacuum pump or a water-xylene azeotrope where thetemperature is preferably maintained under about 35° C. and a vacuum isapplied simultaneously). The presence of water results in the undesiredhydrolysis of the acrylodiethylphosphite or methacrylodiethylphosphiteto a phosphate, releasing the acrylate.

Acrylate or methacrylate groups in the presence of appended phosphitesof Cu are predisposed to self polymerization. Hence, a cooling bath anddilution with more solvent are recommended. A solution temperature ofless than about 15° C. is recommended, but at temperatures lower thanabout 5° C., incomplete phosphite incorporation may be observed andshould be avoided.

The series of PCuX monomers is limited by the number of stable CuXcompounds. The PCuX monomer is typically a colorless or light yellowviscous liquid that should polymerize under the influence of heat orlight.

The number of phosphites per CuX unit varies, depending on X. Forexample, in the case of CuCl there is only one phosphite per CuCl. Inthe case of CuSCN, there are two phosphites per CuSCN, and in the caseof CuSPh there are three phosphites per CuSPh unit.

UV photolysis of the PCuCl monomer gives a green white solid and twophosphates. In other words, Cu was released. The presence ofchlorodiethylphosphate indicates that a homolytic cleavage of the Cu--L¹(e.g., Cu--P) bond has taken place, followed by a rearrangement torelease the phosphate. (See Rxn (a).) The same decomposition reactionswere observed for PCuSCN monomer and PCuSPh monomer. (See Rxn (b) and(c).) ##STR16##

The electrochemical behavior of the PCuX monomers were determined usingcyclic voltammetry. The electrochemical cell contained 10 mL of the PCuXmonomer in 1×10³ M saturated CH₂ Cl₂ solution of tetrabutylammoniumhexafluorophosphate. The reference electrode was a saturated calomelelectrode (SCE), the working electrode was carbon, and the auxiliaryelectrode was Pt. The procedure followed was described in the CV-27Cyclic Voltammograph manual. Electrochemical studies of the monomersgave the following results:

    ______________________________________                                                            Reduction                                                                             Oxidation                                                             Potential                                                                             Potential                                         ______________________________________                                        [H.sub.2 C═C(CH.sub.3)C(O)O](EtO).sub.2 PCuCl                                                   -1.00 eV  1.375 eV                                      {[H.sub.2 C═C(CH.sub.3)C(O)O)](EtO).sub.2 P}.sub.3 CuSPh                                        -1.350 eV 0.935 eV                                      [H.sub.2 C═C(CH.sub.3)C(O)O](EtO).sub.2 PCuSBu.sup.t                                            -1.355 eV 0.875 eV                                      ______________________________________                                    

The electrochemical results are relevant because they demonstrate thatthe Cu compounds can couple with another Cu(+1) compound, Cu₂ O, to giveCu(O) and Cu(+2) complexes (reaction (d)). This can aid in thecontrolled release of both Cu species.

    Cu.sub.2 O+Cu(I) Monomer→Cu(O)+Cu(II)               (d)

Once the compound of formula (I) is formed, as discussed above, thiscompound can then be polymerized with one or more other monomers to forma polymer. Preferably, a methacrylate monomer and a film softeningmonomer, such as an acrylate monomer, are polymerized with a compound offormula (I) to form a terpolymer. Preferably, the compounds of formula(I) with one or more other monomers, such as the film softening monomerand methacrylate monomer, are polymerized by free radical polymerizationexcept in the case where M is Cu(II). Additionally, compounds of formula(I) with one or more monomers, such as the film softening monomer andmethacrylate monomer, can also be polymerized by condensationpolymerization. A solvent should be used such that the polymer remainssoluble in the solvent. Generally, ketone-based solvents are preferredand methyl ethyl ketone is most preferred. The polymerization reactionis preferably initiated by a free radical initiator. Once polymerized,the polymer may have the following repeating unit: ##STR17## However,the monomers are incorporated randomly into the polymer.

Examples of film softening monomers include, but are not limited tosubstituted and unsubstituted acrylate monomers such as: methylacrylate; ethyl acrylate; butyl acrylate; ethyl methacrylate; butylmethacrylate; isobutyl methacrylate; isooctyl acrylate; 2-ethylhexylmethacrylate; nonyl acrytate; nonyl methacrylate; lauryl methacrylate;stearyl methacrylate; dimethylaminoethyl acrylate; dimethylaminoethylmethacrylate; trifluoroethyl methacrylate; 2-methoxyethyl acrylate;2-ethoxyethyl methacrylate; 2-ethylhexyl acrylate; and t-butylaminoethylmethacrylate.

In particular, it has been discovered that it is possible by use ofcertain free radical initiators to polymerize the unsaturation of theacrylate component of the above material. However, polymerizing suchmonomers by a free radical initiator such as those that use hydrogenperoxide or an organic based peroxide, such as a carboxylic acid basedbenzoyl peroxide, will usually lead to oxidation of copper (I) to copper(II) and destruction of the copper-containing monomer.

Preferably, the free radical initiators suitable especially forcopper-containing monomers of this invention include azo type compounds,for example, azonitriles; azoamidines; azo moieties substituted withalkyls; and azo moieties substituted at the alpha carbon withcombinations of one or more of the following: alcohols, esters,nitriles, amides, aminoalcohol, and substituted amines and amidesthereof.

Examples of commercially available azonitriles sold by Wako PureChemical Industries Ltd. are: Azonitrile Compounds;2.2'-Azobis(4-methoxy-2.4-dimethylvalero-nitrile),2.2'-Azobis(2.4-dimethylvaleronitrile),2.2'-Azobis(2-methylpropionitrile), (2.2'-Azobisisobutyronitrile),2.2'-Azobis(2-methylbutyronitrile),1.1'-Azobis(cyclohexane-1-carbonitrile),1-[(1-Cyano-1-methylethyl)azo]formamide(2-(Carbamoylazo)isobutyronitrile),2-Phenylazo-4-methoxy-2.4-dimethyl-valeronitrile, Azoamidine Compounds:2.2'-Azobis(2-methyl-N-phenylpropion-amidine)dihydrochloride,(2.2'-Azobis(2-(N-phenylamidino)propane)dihydrochloride,2.2'-Azobis[N-(4-chlorophenyl)-2-methyipropionamidine]dihyrochloride,(2.2'-Azobis 2-[N-(4-chlorophenyl)amidino]propanel dihydrochloride),2.2'-Azobis[N-(4-hydroxyphenyl)-2-methylpropionamidine]dihydrochloride)(2.2'-Azobis 2-[N-(4-hydroxyphenyl)amidino]propane dihydrochloride,2.2-Azobis[2-methyl-N-(phenylmethyl)-propionamidine]dihydrochloride,2.2'-Azobis[2-(N-benzylamidino)propane]dihydrochloride,2.2'-Azobis[2-methyl-N-(2-propenyl) propionamidine]dihydrochloride,2.2'-Azobis [2-(N-allylamidino)propane]dihydrochloride,2.2'-Azobis(2-methylpropionamidine)dihydrochloride,(2.2'-Azobis(2-amidinopropane)dihydrochloride,2.2'-Azobis[N-(2-hydroxyethyl)-2-methylpropionamidine]dihydrochloride,(2.2'-Azobis 2-N-2-hydroxyethyl)amidino]propane dihydrochloride,Azoamide Compounds: 2.2'-Azobis2-methyl-N-[1,1-bis(hydroxymethyl)-1-hydroxyethyl]propionamide,2.2'-Azobis 2-methyl-N-[1.1-bis(hydroxymethyl)ethyl]propionamide,2.2'-Azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2.2'-Azobis(2-methylpropionamide)dihydrate, (2.2'-Azobis(isobutyramide)dihydrate),Alkylazo Compounds: 2.2'-Azobis(2,4,4-trimethylpentane)(Azodi-tert-octane), 2.2'-Azobis(2-methylpropane) (Azodi-tert-butane)and for azo moieties substituted at the alpha carbon with combinationsof one or more of the following: alcohols, esters, nitriles, amides,aminoalcohol, and substituted amines and amides thereof. Other examplesinclude Dimethyl, 2.2'-azobis(2-methylpropionate) (Dimethyl2.2'-azobisisobutyrate), 4.4'-Azobis(4-cyanovaleric acid),(4.4'-Azobis(4-cyanopentanoic acid)),2.2'-Azobis[2-(hydroxymethyl)propionitrile]

Organic based peroxide initiators, while generally not suitable forpoiymerizing or copolymerizing copper containing monomers of thisinvention, are however suitable for polymerizing other metals within thescope of this invention when they are used in place of copper. Examplesof these alternative initiators are: organosulfonyl peroxides; dialkylor diaryl or alkyl aryl peroxides; diacyl peroxides; ketone peroxides;peroxyketais; peroxydicarbonates; peroxycarbonates; and peroxyesters.

Examples of these materials are available commercially from Elf AtochemNorth America, Inc. under the trade name LUCIDOL. Specific chemicalexamples of some of these materials are: Diacyl peroxides; 2,4-DichloroBenzoyt Peroxide, Diisononanoyl Peroxide, Decanoyl Peroxide, LauroylPeroxide, Succinic Acid Peroxide, Acetyl Peroxide, Benzyol Peroxide,Ketone Peroxide; 2,4-Pentanedione Peroxide, Peroxydicarbonates;Di(n-propyl) Peroxydicarbonate, Di(sec-butyl) peroxydicarbonate,Di(2-ethylhexyl) peroxydicarbonate, Di(2-phenoxyethyl)Peroxydicarbonate, Peroxyesters; α-cumylperoxy Neodecanoate,α-cumylperoxy Pivalate, t-Butylperoxy Neodecanoate,t-Butylperoxypivalate, 2,5-Dimethyl 2,5-di(2-ethylhexanoylperoxy)hexane, t-Butylperoxy-2-ethylhexanoate, t-Butylperoxyiosbutyrate,t-Butylperoxymaleic acid, 2,5-Dimethyl-2,5-di(benzyolperoxy) hexane,t-Butylperoxy Acetate, t-Butylperoxy Benzoate, Di-t-Butyldiperoxyphthalate, t-Amyl peroxy pivalate, Dialkyl Peroxides, DicumylPeroxide, 2,5-Dimethyl-2,5-di(t-butylperoxy)hexane, Di-t-Butyl Peroxide,2,5-Dimethyl-2,5-di(t-butylperoxy)hexyne-3, Hydroperoxides;2,5-Dihydroperoxy-2,5-dimethylhexane, t-Butyl Hydroperoxide,Peroxyketals; 1,1-Di(t-butylperoxy) 3,3,5-trimethyl cyclohexane,1,1-Di(t-butyl-peroxy) cyclohexane, 2, 2-Di(t-butylperoxy)butane,Ethyl-3,3-Di(t-butylperoxy)butyrate.

In addition, one or more of the following substituted or unsubstitutedmonomers can be polymerized with a monomer of formula (I): acrylates;acroleins; acrylonitriles; acrylamides; acryloyl halides; allyls;butadienes; citraconimide; diallyls; isoprenes; iraconic acids;itaconamates; itaconimides; maleic alkylates; maleic anhydrides;maleimides; methacrylamides; alkyl methacrylates; methacrylic acids oranhydrides; oxazolines; pyrrolidones; styrenes; vinyls; and vinylidenehalides. Some typical examples of some of these are: with respect toacrylates: alpha-acetoxy ethyl acrylate; alpha-chloro methyl acrylate;alpha-trifluoromethyl methyl acrylate; benzyl acrylate; ethyl acrylate;ferrocenylmethyl acrylate; isobutyl acrylate; and phenyl acrylate; withrespect to butadiene, 2,3-dichloro butadiene; 2-chloro butadiene;Acrylamide; α-fluoroacrylamide, N-octadecyl-acrylamide, Acrylate;methyl-α-chloro acrylate, methyl, α-fluoromethyl-acrylate, benzylacrylate, ethyl acrylate, ferrocenylmethyl acrylate, isobutyl acrylate,phenyl acrylate, Acrylic acid; α-bromo-acrylic acid, Acrylonitrile;α-trifluoromethyl-acrylonitrile, Allyl; alcohol allyl, Butadiene;2,3-dichloro-butadiene, 2-chloro-butadiene, Citraconimide;N-benzyl-citraconimide, N-butyl-citraconimide, N-isobutylcitraconimide,Diallyl; melamine diallyl, phthalate diallyl, Diallylcyanamide;Isoprene; 3-acetoxy-isoprene, Isopropenyl acetate; ItaconamateN-phenyl-ethyl; Itaconate dibutyl; Iraconic acid; Itaconimide, N-benzyl;Maleimide; N-(4-hydroxyphenyl)-maleimide, N-benzyl-maleimide,N-butyl-maleimide, N-phenyl-maleimide, Methacrylamide;N-methoxymethyl-methacrylamide, N-phenyl-methacrylamide,Alkylmethacrylates; benzyl alkylmethacrylate, chloromethylalkylmethacrylate, cyanomethyl alkylmethacrylate, glycidylalkylmethacrylate, 2-hydroxyethyl alkylmethacrylate, 2-hydroxypropylalkylmethacrylate, 2-phenethyl alkylmethacrylate, Methacrylic acid;anhydride methacryiic, Oxazolidone; N-vinyl oxazolidone, Pyrrotidone;α-methylene-N-methyl-pyrrolidoe, N-vinyl-pyrrolidone,1-benzyl-3-methylene-5 methyl pyrrolidone, Styrene; α-methyl-styrene,2,4,6-trimethyl-styrene, 2,5-dichloro-styrene, m-bromo-styrene,m-chloro-styrene, m-methyl-styrene, p-bromo-styrene,p-chloromethyl-styrene, p-N,N-dimehtylamino-styrene, Vinyl; acetatevinyl, benzoate vinyl, bromide vinyl, butyrate vinyl, chloride vinyl,ether vinyl, ethyl ether vinyl, ethyl ketone vinyl, ethyl oxalate vinyl,ethyl sulfide vinyl, ethyl sulfoxide vinyl, phenyl ketone vinyl,propionate vinyl, sulfone vinyl, vinylferrocene, vinylhydroquinone,dibenzoate vinylhydroquinone, Vinylidene; chloride vinylidene, cyanidevinylidene, Vinylisocyanate; Vinyltrimethylsilane.

The choice of the monomers is dependent on the properties required foreach controlled release application. For example, polymers for marineantifoulant applications must give a flexible film with good mechanicalintegrity. Therefore, the monomer of formula (I) must be polymerizedwith a rubbery monomer for flexibility (e.g., butyl acrylate) and a hardmonomer for good mechanical properties (e.g., methyl methacrylate).

Polymerization of the PCuCl and other transition metal monomers of thisinvention with methyl acrylate (MA), methyl methacrylate (MMA) and butylacrylate (BA) in MEK gives a polymer solution with Mw of about 50,000 toabout 60,000.

The polymer acts as a binder which is held in suspension by a solventsuch as a ketone, preferably methylethyl ketone. Then, pigments, dyes,and other biocides are added in manners known to those skilled in theart. A description of such components and ways to add such components toform the paint is described in a technical book entitled MarineBiodeterioration: An Interdisciplinary Study, J. D. Costlaw and R. C.Tipper, Eds., Naval Institute Press, Annapolis, Md., 1984, incorporatedherein by reference, with particular emphasis on the chapter titled "TheChemical and Physical Characterization of Marine Coatings ContainingOrganotin Antifoulants" by M. L. Good and C. P. Monaghan.

Once formed into a paint, the paint can be applied to a surface such asa hull, and upon application, the solvent (e.g., ketone) evaporatesleaving the polymer with other ingredients. Preferably, the solvent thatis used has a long alkyl chain which permits a slow evaporation of thesolvent which assists in avoiding trapping of the solvent beneath theinterior layers of the paint.

The preferred organometallic polymers made in accordance with thisinvention achieve the following:

1. The polymer is solvent soluble, for easy application.

2. The polymer solution provides a clear, hard film with enoughflexibility to coat a ship's surface.

3. The film undergoes at least some surface hydrolysis to release ametal, to become a material that either dissolves or swells and isattritted or dissolved off to provide a fresh and new polymer layer thatis preferably smooth to preserve a ship's fuel efficiency.

The polymers of the present invention are also capable of releasing in acontrolled manner an active agent. Controlled release systems permit anactive chemical agent (e.g. Cu₂ O; Manganese ethylenebisdithiocarbamate(Maneb); Zinc dimethyldithiocarbamate (Ziram);2(Cyclopropylamino)-4-isobutylamino-6-methylthio-S-triazine;N'(3,4-dichlorophenyl)-N,N-dimethyl urea (Diuron; Zincethylenebisdithiocarbamate (Zineb); N-(fluorodichloromethylthio)phthalimide Fluorofolpet);N,N-dimethyl-N'-phenyl-N'-(fluorodichloro-methylthiosulphamide(Dichlorofluanide, Euparen); Tetramethylthiuram disulfide (Thiram);Methylene bis(thiourea); 4-Butyl catechol; Captan; Zinc dimethyldithiocarbamate;2-Methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine;2,4,5,6-Tetrachloroisophthalonitrile; N,N-Dimethyl-N'-dichlorophenylurea; Copper thiocyanate; 4,5-Dichloro-2-n-octyl-3(2H) isothiazolone;N-Fluorodichloromethylthio-phthalimide;N,N-Dimethyl-N'-phenyl-N'-fluorodichloromethylthio-sulfamide;2-Pyridinethiol-1-oxide zinc salt; Tetramethyl thiuram disulfide;Copper-nickel (10%) solid solution alloy; 2,4,6-Trichlorophenylmaleimide; 2,3,5,6-Tetrachloro-4-methylsulfonyl pyridine;3-Iodo-2-propenyl butyl carbamate; Diiodomethyl p-toluyl sulfone;Bis-(dimethyldithiocarbamoyl zinc)ethylene bis-dithiocarbamate; Pyridinetriphenylboran; Zinc-2-pyridinethiol-N-oxide (Zinc Omadine) (Zinc saltof 1-hydroxy-2-pyridinethione); Tetrachloroisophthalonitrile (NuoCide960s) (Chlorothalonil);1-Methylthio-3-(t-butylamino)-5-(cyclopropylamino)-S-triazine (Irgarol1051);4,5-Dichloro-2-n-octyl-3-(2H)-isothiozolone/chloro-2-n-octyl-3-(2H)-isothiazolone7/1 (Anti-Foulant 3-9211M); Isothiazolone, an organosulfur biocide (Rohm& Haas, Philadelphia)) to be transferred to a specified target at a rateand duration designed to accomplish an intended effect. These systemshave found growing use in many areas, for example, in pharmaceuticals,catalysts, pesticides, and antifoulants. For purposes of the presentinvention, the basic components of a controlled release system includethe active agent and the polymer matrix which regulates the activeagent's release. The use of the polymer system is dependent on itsproperties and these can be tailor-made for each controlled releaseapplication. The controlled release system that is particularly usefulwith the compounds of the present invention are "erodable" systems. Inparticular, the active agent is blended so that it either dissolves in,is physically dispersed in, or is chemically bound to the polymermatrix. The polymer used is either soluble or degrades during use andthe active agent is released by a combination of diffusion andliberation due to erosion. The metal containing polymer systems asdescribed in this invention refer to a delivery system which willrelease an active agent through surface erosion due to an environmentalagent such as water.

The main advantage of controlled release systems is that they allow muchless of the active agent to be used more effectively over a given periodof time. For example, pesticides or biocides can be released in acontrolled manner fox an extended period of time. A particular exampleis the marine antifoulant controlled release systems of the presentinvention which have extended the lifetime of ship's coatings from twoyears to five years.

Furthermore, the present invention relates to metal complexes having theformula (II): ##STR18## where the definitions of M, x, L², n, and R⁴ arethe same as in formula (I). Compounds of formula (II) can be used asadditives to such compositions as paint formulations in order to preventfouling on surfaces susceptible to fouling. Manners in which the metalcomplex is incorporated in compositions such as paint formulations aswell as means to apply the composition to surfaces (e.g., ship hulls)are known to those skilled in the art.

In the examples set forth below, there is a comparison of theeffectiveness of introducing copper into a polymer such as thatdisclosed above which initially does not contain copper.

To obtain optimal film forming properties the average molecular weightof polymers, measured in accordance with ASTM method number D 5296-92,made from monomers made and used in accordance with this invention arepreferably in the range of about 5000 to 200,000; more preferably in therange of about 10,000 to 75,000.

Based on this description, and the specific examples that follow, oneskilled in the art can generally follow the procedures described belowin preparing all of the compounds of formula (I).

EXAMPLES

Monomer Syntheses

Example 1 Synthesis of [H₂ C═C(CH₃)C(O)O]P(OEt)₂

Methacrylic acid in slight excess was reacted with NaOH in xylene togive Na acrylate and H₂ O. The solid Na acrylate was collected andwashed with xylene and heptane until methacrylic acid could not bedetected and then any remaining traces of H₂ O were removed undervacuum. Table 1 sets forth the precise details of the synthesis.

                  TABLE 1                                                         ______________________________________                                        Sodium Acrylate Synthesis                                                     ______________________________________                                        Materials     M.W.      Moles   Charged (g)                                   ______________________________________                                        Methyacrylic Acid                                                                           86.09     1.18    100                                           Sodium Hydroxide                                                                            40.00     1.125    45                                           Xylene        106.17            650                                           Xylene wash                     400                                           Heptane Wash                    350                                           Total Charge:                   1545                                          ______________________________________                                        1. Charge 650 g xylene into a 3 L four-necked flask                           with xylene.                                                                  2. Degas xylene.                                                              3. Charge 100 g methacrylic acid into the reaction flask.                     4. Add 45 g sodium hydroxide in three equivalent over 3 h.                    5. Stir for 2 days under nitrogen.                                            6. Collect the sodium acrylate in a Schlenk filter.                           7. Wash the sodium acrylate three times with xylene                           (total: 400 g) and three times for heptane                                    (total: 350 g).                                                               8. Pump off residual solvents and water. Dry under vacuum                     for 2 days.                                                                   ______________________________________                                    

A dilute solution of Na acrylate with chlorodiethylphosphite in heptanewas then reacted over several hours to give acrylodiethylphosphite andNaCl. The reaction was monitored to ensure that all of thechlorodiethylphosphite was consumed. A slight excess (1.15) of the Naacrylate was used. The NaCl was filtered off to give a heptane solutionof acrylodiethylphosphite. This phosphite was reacted in situ with CuClas discussed in Example 2 below. Table 2 sets forth the precise detailsof this synthesis.

The phosphite was characterized by: GC-MS (parent ion=206.10), IRspectroscopy [ν(CO)=1708 cm⁻¹ and ν(P--O)=1027 cm⁻¹), and ³¹ P-NMRspectroscopy (134 ppm).

Example 2 Synthesis of [H₂ C═C(CH₃)C(O)O](EtO)₂ PCuCl

CuCl was added to the above heptane solution of acrylodiethylphosphite,which was cooled to 2°-5° C. A viscous purple layer separated out andwas isolated as a purple oil. The viscous purple oil was stirred andresulted into a brown oil. The [H₂ C═C(CH₃)C(O)O](EtO)₂ PCuCl complexthus formed, was washed with heptane. Unreacted CuCl was filtered offfrom the solution of the complex in methylethylketone. Table 2 also setsforth the precise details of this synthesis.

                  TABLE 2                                                         ______________________________________                                        CuCl Monomer Synthesis                                                        ______________________________________                                        Materials     M.W.      Moles   Charged (g)                                   ______________________________________                                        Sodium Acrylate                                                                             108.08    139     15                                            CIP(OEt).sub.2                                                                              156.55    124     19                                            CuCl           98.99     91      9                                            Heptane                         200                                           Heptane wash                    50                                            Methylethylketone               16                                            Total Charge:                   309                                           ______________________________________                                        1. Dry glassware in oven. Assemble glassware and dry                          further with heat gun.                                                        2. Charge sodium acrylate into reaction flask under N.sub.2.                  3. Add 200 g dry heptane to reaction flask via cannula.                       4. Maintain reaction solution at 2-5° C. (cold water bath).            5. Agitate the solution and syringe CIP(OEt).sub.2 dropwise.                  Keep the solution temperature at below 10° C.                          6. Continue stirring for two hours. NOTE: Reaction is                         complete when no CIP(OEt).sub.2 is detected in the GC-MS                      spectrum.                                                                     7. Filter off the NaCl by product and cool reaction                           solution to †10° C.                                             8. Add CuCl to reaction solution over 1 h. Keep the                           solution temperature at 10-13° C. during CuCl addition.                NOTE: The product is a purple oil which turns brown                           with continued stirring.                                                      9. Syringe off the heptane layer.                                             10. Add 16 g of MEK and filter. NOTE: Characterize the                        CuCl monomer by .sup.1 H-- and .sup.31 P-NMR spectroscopy.                    11. Use the MEK solution of the CuCl monomer for the                          polymerization. IF the CuCl monomer will not be used                          immediately, store the solution in the freezer.                               ______________________________________                                    

For CuSPh and CUSBu^(t) Synthesis the procedure followed was similar tothat given in ref. 1.

Elemental analyses disclosed that the mole ratio of P:Cu:Cl was 1:1:1.The NMR spectrum indicated that the phosphite was intact and bonded tothe Cu. The peak had shifted upfieid from 134 to 120 ppm and was broaddue to coupling the phosphorus with ⁶³ Cu (abundance=69.1%) and ⁶⁵ Cu(abundance=30.9%), both of which had spins of 3/2. The IR spectrum gavea ν(CO) peak at 1720 cm⁻¹ which had shifted from 1708 cm⁻¹.

Example 3 Synthesis of {[H₂ C═C(CH₃)C(O)O](EtO)₂ P}2CuSCN

CuSCN was suspended in heptane and mixed with a heptane solution of [H₂C═C(CH₃)C(O)O]P(OEt)₂. The phosphite in slight (about 10%) excess wasprepared in situ and reacted by stirring at room temperature for atleast 12 hours. The resulting {[H₂ C═C(CH₃)C(O)O](EtO)₂ P}₂ CuSCN wasisolated as a filtered yellow oil.

The IR spectrum gave a ν(CO) at 1723 cm⁻¹, a phosphite band at 1024 cm⁻¹and a u(SCN) band at 2115 cm⁻¹.

Example 4 Synthesis of {[H₂ C═C(CH₃)C(O)O](EtO)₂ P}₃ CuSPh

CuSPh was prepared from a 1:2 molar mixture of Cu₂ O and HSPh in dryethanol. The mixture was heated to reflux until bright yellowprecipitate CuSPh was formed and substantially all of the Cu₂ O hadreacted to the phenyl thiol of copper. The precipitate was washed withethanol and xylene.

The CuSPh compound was then reacted with [H₂ C═C(CH₃)C(O)O]P(OEt)₂ in aheptane solvent. A yellow solution resulted which was susceptible tolight decomposition with time. The IR spectrum gave multiple peaks dueto ν(CO) at 1791, 1733, and 1717 cm⁻¹.

Example 5 CuCl-MMA-BA Terpolymer Synthesis

Table 3 sets forth details of the polymerization of CuCl monomer withmethyl methacrylate (MMA) and butyl acrylate (BA). The composition ofthe solids in the starting solution was 27 mol % CuCl monomer, 65 mol %MMA, and 8 mol % butyl acrylate (BA). The final component of thesolution was 80 wt % MEK. The BA was added to give the polymer moreflexibility, thus offsetting the rigidity of the MMA component.

                  TABLE 3                                                         ______________________________________                                        Polymerization of CuCl Monomer with MMA and BA                                ______________________________________                                                      M.W.                                                            Materials     (g/mol)   Moles   Charged (g)                                   ______________________________________                                        CuCl monomer  305.2     0.085   26                                            Methyl        100.12    0.205   20.5                                          methacrylate                                                                  (MMA)                                                                         Butyl Acrylate                                                                              128.17    0.025   3.2                                           (BA)                                                                          AIBN          164.21    0.006   1                                             Methylethylketone                                                                            72.11    0.006   199                                           (MEK)                                                                         Total Charge:                   249.7                                         ______________________________________                                        1. Charge 20.5 g MMA, 3.2 g BA, and 175 g MEK into a                          500 mL, four-neck reaction flask.                                             2. Degas the solution for 30 minutes.                                         3. Place the flask in a heated mantled air-jack.                              4. Heat flask to 80° C. NOTE: A vigorous agitation is                  necessary to minimize insoluble solids formation.                             5. Add 10 mL MEK solution of AIBN via a syringe                               pump over 4 h. At the same time, add solution                                 of 20 mL MEK and CuCl monomer via a syringe                                   pump over 3 h.                                                                6. Continue heating to 80° C. for an additional 10 h.                  7. Retain the soluble ortion of the polymer solution                          NOTE: Characterize for LOD (loss on dissolution) and by                       .sup.1 H-- and .sup.31 P-NMR spectroscopy.                                    ______________________________________                                    

Example 6 Erosion Studies

The film forming properties have been demonstrated using the terpolymersof the PCuCl monomer with methyl methacrylate and butyl acrylate. Apolymer solution synthesized using the method given in Example 5 wasused. The MEK solution of the polymer was placed on sanded fiberglasspanels and the MEK was allowed to evaporate at ambient temperatures overthree days. A hard film resulted.

The erosion capability of the polymer binder was tested in artificialseawater. The polymer solution was formulated with cuprous oxide andBentone 27 in the following weight ratios:

    ______________________________________                                        Ingredient      Pts/wt                                                        ______________________________________                                        Polymer Solids  10.00                                                         Cuprous oxide   20.00                                                         Bentone 27      1.0                                                           ______________________________________                                    

The above mixture was poured into a tin and mixed using a paint shaker.Cuprous oxide is a cotoxicant that is typically added to mostantifoulant formulations. The low solids content of the polymer solutionmade it necessary to add a thickener (Bentone 27) in order to preventthe cuprous oxide from settling out of the solution. This pigmentedsolution was placed on a sanded fiberglass panel and allowed to dry over3 days. The panels were placed in a circulating tank of artificialseawater and were monitored over time. The following results wereobserved.

1. Small green spots were observed after one day of immersion anddisappeared with time. A uniform film was obtained afterward and surfaceerosion was observed.

2. After two weeks of immersion testing, the panel was placed in abeaker of moving artificial seawater for three days. Testing of thewater solution for % Cu release indicated that it was comparable to theorganotin control (1.84 ppm vs. 1.11 ppm).

3. The film had good integrity and good adhesion to the panel.

Several different factors were determined as a result of thispolymerization of the CuCl monomer:

1. The initiator generally required was an AIBN(2,2'-azobis(isobutyronitrile)) type compound. Benzoyl peroxide tendedto oxidize the Cu(I) to Cu(II), i.e., the solution turned from colorlessto a dark purple. A minimum of ˜0.5 mol % of AIBN, based upon the totalnumber of moles of all monomers present, is generally required forpolymerization to be observed.

2. Preferably, the reaction temperature is preferably about 80° C.

3. The addition rate of both AIBN and CuCl are important and preferablyare added separately at about the same rate and time to the reactionmedium that contains a ketone solvent, such as acetone or methyl ethylketone, and a comohomer, MMA and/or BA. Addition rates that take inexcess of several hours are generally required depending upon thecomonomer. The quantity of AIBN used is between 0.5 and 2.0 molepercent, as based upon the total number of moles of all monomerspresents. Sometimes an insoluble solid will form. An NMR spectra of aportion of the insoluble solid revealed that a polymer had formed.

Specific compositions, methods, or embodiments discussed herein areintended to be only illustrative of the claimed invention. Variations ofany of these would be apparent to one skilled in the art based upon theteachings contained herein and are intended to be within the scope ofthe present invention. For example, only copper containing polymers areexpressly discussed in the examples. Others are made substantially thesame way by substituting a different metal in place of all or a portionof the copper in the syntheses discussed.

For example, it is within the intended scope of this invention toinclude known antifoulant materials, such as Cu₂ O or CuSCN, within theresin compositions as useful additives provided that they are compatibleor can be made so with the resin matrix.

For still another example, use of the fact that acrylic-phosphite esterscontaining copper (I) as a coordinated species can be hydrolyzed andoxidized to phosphate esters and then phosphoric acid functional groups,as a method for controlling pH and rates of hydrolysis depending uponthe length of the organic component of the phosphate ester.Additionally, controlling the amount of hydrolysis after the polymer hasbeen formed and before incorporating the material into a final coatingaffords a useful route for controlling availability of different formsof antifoulant metal, or changing the polarity and/or hydrolyricproperties of the polymer.

Other embodiments of the present invention will be apparent to thoseskilled in the art from consideration of the specification and practiceof the invention disclosed herein. It is intended that the specificationand examples be considered as exemplary only, with a true scope andspirit of the invention being indicated by the following claims.

What is claimed is:
 1. A compound of formula (I) ##STR19## wherein L¹ isan element of Groups 13-16 of the Periodic Table;L² is a neutral ligand;M is a transition element or a metal element of Groups 13-16 of thePeriodic Table; n represents the number of coordination sites of M; xrepresents the oxidation state of M, R¹ is a polymerizable group; R² andR³ are independently selected from the group consisting of an alkyl ofup to 15 carbons; an aryl of up to 30 carbons; an alkoxy or thioalkyl ofup to 15 carbons; an aryloxy or thioaryl of up to 20 carbons; an oxygenor sulfur containing heterocycle of up to 25 carbons; an amine; anamide; and a nitrogen heterocycle of up to 25 carbons with the provisothat L is not N; or R² and R³ having the same definitions as above,interconnect to form a chelating ligand; R⁴ is an anionic ligand andwhen x is greater than 1, each R⁴ is the same or different; and m is 1,with the proviso that m is 2 when M is Cu, x is 1, L¹ is phosphorus, L²is not present and R⁴ is cyanate; and m is 3 when M is Cu, x is 1, L¹ isphosphorus, L² is not present, and R⁴ is a thioalkyl having up to 15carbons or a thioaryl having up to 25 carbons; and also with the provisothat when M is Rh, R¹ is a polymerizable group having a (═CH₂) group. 2.The compound of claim 1, wherein R⁴ is selected from the groupconsisting of a halogen, a cyanate, an isocyanate, a thiocyanate, athioalkyl of up to 15 carbons; a thioaryl of up to 25 carbons; a sulfurcontaining heterocycle of up to 25 carbons; an alkoxide of up to 15carbons; an aryloxide of up to 25 carbons; an oxygen containingheterocycle of up to 25 carbons; a cyclopentadienyl of up to 30 carbons;and an acetylacetonate optionally substituted by a halogen.
 3. Thecompound of claim 1, wherein R¹ has the formula ##STR20## wherein R⁶ isa hydrogen; an alkyl of up to 25 carbons; an olefin of up to 25 carbons;andR⁷ is a hydrogen; an alkyl of up to 25 carbons; an aryl of up to 25carbons; a halogen; a carboxylic group of up to 25 carbons; an amidegroup of up to 25 carbons; a cyanate; an isocyanate; or a thiocyanate.4. The compound of claim 1, wherein R¹ is a cyclic monomer polymerizablethrough ring opening polymerization or through a double bond within thering.
 5. The compound of claim 4, wherein the cyclic monomer has threeto eight members selected from the group consisting of a carbon; acarbonyl; an oxygen; a phosphorus; and an amide; with the proviso thatthe total number of carbons in the cyclic monomer does not exceed
 40. 6.The compound of claim 1, wherein R¹ is a monomer with at least onecoreactive functional group.
 7. The compound of claim 6, wherein themonomer with at least one coreactive functional group has one of thefollowing formulas:H₂ N--R⁸ --NH₂ ; HO₂ C--R⁹ ----CO₂ H; H₂ N--R¹⁰ --CO₂H; HO--R¹¹ --OH; Cl--R¹² --Cl; or ClOC--R¹³ --COCl; wherein R⁹, R¹⁰,R¹¹, R¹², and R¹³ are independently selected from the group consistingof an alkyl of up 25 carbons; an aryl of up to 25 carbons; a silane ofup to 25 carbons; a nitrogen heterocycle of up to 25 carbons; andwherein R⁸ is a group selected from the above or is carbonyl.
 8. Thecompound of claim 1, wherein L¹ is nitrogen, phosphorus, arsenic,antimony, or bismuth.
 9. The compound of claim 8, wherein L¹ isphosphorus.
 10. The compound of claim 1, wherein M is copper, zinc, ortin.
 11. The compound of claim 10, wherein M is copper.
 12. The compoundof claim 11, wherein M is copper (I).
 13. The compound of claim 1,wherein M is copper (I), n is 2, and R⁴ is Cl.
 14. A compound of claim1, wherein M is Cu(I), R⁴ is Cl, x is 2, n is 3, m is 1, L¹ is P, R² andR³ are ethoxy groups, and R¹ is a methacrylate group.
 15. A controlledrelease composition comprising a compound of claim
 1. 16. Thecomposition of claim 15, further comprising an active agent.
 17. Thecompound of claim 1, where L¹ is an element of Group 13 of the PeriodicTable.
 18. The compound of claim 1, wherein L¹ is an element of Group 14of the Periodic Table.
 19. The compound of claim 1, wherein L¹ is anelement of Group 16 of the Periodic Table.
 20. The compound of claim 1,wherein M is a metal element of Group 13 of the Periodic Table.
 21. Thecompound of claim 1, wherein M is a metal element of Group 14 of thePeriodic Table.
 22. The compound of claim 1, wherein M is a metalelement of Group 15 of the Periodic Table.
 23. The compound of claim 1,wherein M is a metal element of Group 16 of the Periodic Table.
 24. Thecompound of claim 1, wherein M is a transition element of the PeriodicTable.
 25. The compound of claim 1, wherein R¹ is an acrylate ormethacrylate group.
 26. The compound of claim 1, wherein R² and R³,which can be the same or different, are an alkyl or alkoxy group of upto 15 carbons or an aryl or aryloxy group of up to 25 carbons.
 27. Thecompound of claim 1, wherein R⁴ is a halogen, a cyanate, an isocyanate,or a thiocyanate.
 28. The compound of claim 1, wherein L² is a trivalentphosphorus, trivalent arsenic, or a trivalent antimony compound or adivalent sulfur, divalent selenium or a divalent tellurium compound whenbonded to three substituents for trivalent compounds or two substituentsfor divalent compounds excluding the bond to M.
 29. The compound ofclaim 1, wherein L² is a substituted or unsubstituted aryl or alkylisocyanide; a carbonyl or carbon monoxide; a thiocarbonyl or carbonmonosulfide; a nitrosyl; a substituted or unsubstituted amine; a nitrilewith a substituted or unsubstituted alkyl or aryl; a coordinatingsolvent; a substituted or unsubstituted unsaturated alkyl or aryl whichbonds to the M mainly through a pi-bond.
 30. The compound of claim 1,represented by formula (II): ##STR21## wherein R¹⁵ represents a hydrogenor a linear alkyl group of up to 6 carbons, and R², R³, L², M, R⁴, x, n,and m have the same meanings as in formula (I).
 31. The compound ofclaim 1, represented by the formula: ##STR22## wherein X is Cl, SCN, orthiophenyl and m=1 when X is Cl, m=2 when X is SCN, and m=3 when X isthiophenyl.
 32. The compound of claim 1, wherein R² and R³ interconnectto form a chelating ligand.
 33. The compound of claim 32, wherein saidchelating ligand has the structure ##STR23## wherein R² and R³ are alkylor alkoxy groups of up to 15 carbon atoms; or aryl or aryloxy groups ofup to 25 carbons; R¹⁴ is an alkyl group of up to 6 carbons or representsa bond between R² and R³, and R¹ is as defined in claim
 1. 34. Thecompound of claim 1, wherein R⁴ is an alkyl group, a thioalkyl having upto 15 carbons, a thioaryl having up to 25 carbons, a sulfur containingheterocycle with up to 25 carbons, an aryloxide with up to 25 carbons,an alkoxide with up to 15 carbons, an oxygen containing heterocycle withup to 25 carbons, a cyclopentadienyl with up to 30 carbons, or anacetylacetonate with optional substitution of at least one of any of thehydrogens on any of the carbons therein with a halogen.
 35. The compoundof claim 1, wherein said alkyl of up to 15 carbons is a substitutedalkyl group wherein at least one hydrogen is replaced with at least onehalogen; at least one oxygen, nitrogen, or sulfur, wherein the oxygenoptionally has at least one additional carbon, nitrogen, or sulfurattached to the oxygen, the nitrogen optionally has at least oneadditional carbon, nitrogen, or sulfur attached to the nitrogen, or thesulfur optionally has at least one additional carbon, nitrogen, orsulfur attached to the sulfur.
 36. The compound of claim 35, whereinsaid substituted alkyl group is an amine, an alcohol, an acid, an ester,a ketone, a sulfide, a sulfone, a sulfoxide, an isocyanate, a cyanate, athiocyanate, a nitrile, or a nitrosone.
 37. The compound of claim 1,wherein said aryl of up to 30 carbons is a substituted aryl groupwherein at least one nitrogen-containing ligand, at least oneoxygen-containing ligand, at least one sulfur-containing ligand, or analkyl group is added to at least one aryl ring carbon.
 38. The compoundof claim 3, wherein said alkyl of up to 25 carbons is a substitutedalkyl group wherein at least one hydrogen is replaced with at least onehalogen, at least one oxygen, nitrogen, or sulfur, wherein the oxygenoptionally has at least one additional carbon, nitrogen, or sulfurattached to the oxygen, the nitrogen optionally has at least oneadditional carbon, nitrogen, or sulfur attached to the nitrogen, or thesulfur optionally has at least one additional carbon, nitrogen, orsulfur attached to the sulfur.
 39. The compound of claim 38, whereinsaid substituted alkyl group is an amine, an alcohol, an acid, an ester,a ketone, a sulfide, a sulfone, a sulfoxide, an isocyanate, a cyanate, athiocyanate, a nitrile, or a nitrosone.
 40. The compound of claim 3,wherein said aryl of up to 25 carbons is a substituted aryl groupwherein at least one nitrogen-containing ligand, at least oneoxygen-containing ligand, at least one sulfur-containing ligand, or analkyl group is added to at least one aryl ring carbon.
 41. The compoundof claim 7, wherein said alkyl of up to 25 carbons is a substitutedalkyl group wherein at least one hydrogen is replaced with at least onehalogen, at least one oxygen, nitrogen, or sulfur, wherein the oxygenoptionally has at least one additional carbon, nitrogen, or sulfurattached to the oxygen, the nitrogen optionally has at least oneadditional carbon, nitrogen, or sulfur attached to the nitrogen, or thesulfur optionally has at least one additional carbon, nitrogen, orsulfur attached to the sulfur.
 42. The compound of claim 41, whereinsaid substituted alkyl group is an amine, an alcohol, an acid, an ester,a ketone, a sulfide, a sulfone, a sulfoxide, an isocyanate, a cyanate, athiocyanate, a nitrile, or a nitrosone.
 43. The compound of claim 7,wherein said aryl of up to 25 carbons is a substituted aryl groupwherein at least one nitrogen-containing ligand, at least oneoxygen-containing ligand, at least one sulfur-containing ligand, or analkyl group is added to at least one aryl ring carbon.